The present paper reports an experimental study aimed at characterizing the effects of heat transfer on the secondary atomization, which occurs during droplet impact on hot surfaces at conditions reproducing those occurring at fuel injection in internal combustion engines. The experiments consider single isooctane and water droplets impacting at different angles on a stainless steel surface with known roughness and encompass a range of Weber numbers from 240 to 600 and heat transfer regimes from the film-vaporization up to the Leidenfrost regime. The mechanisms of secondary breakup are inferred from the temporal evolution of the morphology of the impact imaged with a CCD camera, together with instantaneous measurements of droplet size and velocity. The combination of a technique for image processing with a phase Doppler instrument allows evaluating extended size distributions from 5.5 μm up to a few millimetres and to cover the full range of secondary droplet sizes observed at all heat transfer regimes and impaction angles. Temporal evolution of the size and velocity distributions are then determined. The experiments are reported at impact conditions at which disintegration does not occur at ambient temperature. So, any alteration observed in droplet impact behavior is thermally induced. The analysis is relevant for port fuel injection systems, where droplets injected to impact on the back surface of the valves, behave differently depending on fuel properties, particularly when the use of alcohols is considered, even as an additive to gasoline.